Charge neutrality breakdown in confined aqueous electrolytes : theory and simulation

• Autor(a) principal: Colla, Thiago Escobar
• Data de Publicação: 2016
• Outros Autores: Girotto, Matheus, Santos, Alexandre Pereira dos, Levin, Yan
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Repositório Institucional da UFRGS
• Texto Completo: http://hdl.handle.net/10183/170565
• topic: Eletrólitos; Método de Monte Carlo; Teoria do funcional de densidade

We study, using Density Functional theory (DFT) and Monte Carlo simulations, aqueous electrolyte solutions between charged infinite planar surfaces, in contact with a bulk salt reservoir. In agreement with recent experimental observations [Z. Luo et al., Nat. Commun. 6, 6358 (2015)], we find that the confined electrolyte lacks local charge neutrality. We show that a DFT based on a bulk-HNC expansion properly accounts for strong electrostatic correlations and allows us to accurately calculate the ionic density profiles between the charged surfaces, even for electrolytes containing trivalent counterions. The DFT allows us to explore the degree of local charge neutrality violation, as a function of plate separation and bulk electrolyte concentration, and to accurately calculate the interaction force between the charged surfaces.